EP3131854A1 - Slurry biocide - Google Patents
Slurry biocideInfo
- Publication number
- EP3131854A1 EP3131854A1 EP15779397.7A EP15779397A EP3131854A1 EP 3131854 A1 EP3131854 A1 EP 3131854A1 EP 15779397 A EP15779397 A EP 15779397A EP 3131854 A1 EP3131854 A1 EP 3131854A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluid
- pipeline
- oxidizing biocide
- corrosion
- biocide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003139 biocide Substances 0.000 title claims abstract description 122
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 100
- 239000002002 slurry Substances 0.000 title claims abstract description 43
- 230000001590 oxidative effect Effects 0.000 claims abstract description 100
- 239000012530 fluid Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 46
- 244000005700 microbiome Species 0.000 claims abstract description 29
- 230000002906 microbiologic effect Effects 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 238000005260 corrosion Methods 0.000 claims description 95
- 230000007797 corrosion Effects 0.000 claims description 95
- 239000003112 inhibitor Substances 0.000 claims description 42
- -1 nitrogenous bromine compound Chemical class 0.000 claims description 19
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 14
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 12
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 9
- 230000003628 erosive effect Effects 0.000 claims description 7
- 239000004155 Chlorine dioxide Substances 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000013535 sea water Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940077239 chlorous acid Drugs 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 35
- 238000011282 treatment Methods 0.000 abstract description 10
- 206010061217 Infestation Diseases 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 238000012360 testing method Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 15
- 239000003784 tall oil Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 241000894006 Bacteria Species 0.000 description 11
- CFQZKFWQLAHGSL-FNTYJUCDSA-N (3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e)-octadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoic acid Chemical compound OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C CFQZKFWQLAHGSL-FNTYJUCDSA-N 0.000 description 9
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 8
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000013638 trimer Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 238000010979 pH adjustment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 4
- UUIVKBHZENILKB-UHFFFAOYSA-N 2,2-dibromo-2-cyanoacetamide Chemical compound NC(=O)C(Br)(Br)C#N UUIVKBHZENILKB-UHFFFAOYSA-N 0.000 description 4
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000386 microscopy Methods 0.000 description 4
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- XSXIVVZCUAHUJO-AVQMFFATSA-N (11e,14e)-icosa-11,14-dienoic acid Chemical compound CCCCC\C=C\C\C=C\CCCCCCCCCC(O)=O XSXIVVZCUAHUJO-AVQMFFATSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000539 dimer Chemical class 0.000 description 3
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 150000003752 zinc compounds Chemical class 0.000 description 3
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 2
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 2
- DFJAXEWDHVOILU-UHFFFAOYSA-N (5Z,9E)-5,9-Octadecadienoic acid Natural products CCCCCCCCC=CCCC=CCCCC(O)=O DFJAXEWDHVOILU-UHFFFAOYSA-N 0.000 description 2
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 description 2
- CFKMVGJGLGKFKI-UHFFFAOYSA-N 4-chloro-m-cresol Chemical class CC1=CC(O)=CC=C1Cl CFKMVGJGLGKFKI-UHFFFAOYSA-N 0.000 description 2
- HXQHFNIKBKZGRP-JRVLCRGASA-N 5,9,12-octadecatrienoic acid Chemical compound CCCCC\C=C\C\C=C\CC\C=C\CCCC(O)=O HXQHFNIKBKZGRP-JRVLCRGASA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 2
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 235000021297 Eicosadienoic acid Nutrition 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 235000021319 Palmitoleic acid Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- HXQHFNIKBKZGRP-UHFFFAOYSA-N Ranuncelin-saeure-methylester Natural products CCCCCC=CCC=CCCC=CCCCC(O)=O HXQHFNIKBKZGRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 2
- 229940118781 dehydroabietic acid Drugs 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 2
- 229960004488 linolenic acid Drugs 0.000 description 2
- JWZXKXIUSSIAMR-UHFFFAOYSA-N methylene bis(thiocyanate) Chemical compound N#CSCSC#N JWZXKXIUSSIAMR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VUWCWMOCWKCZTA-UHFFFAOYSA-N 1,2-thiazol-4-one Chemical class O=C1CSN=C1 VUWCWMOCWKCZTA-UHFFFAOYSA-N 0.000 description 1
- TUBQDCKAWGHZPF-UHFFFAOYSA-N 1,3-benzothiazol-2-ylsulfanylmethyl thiocyanate Chemical compound C1=CC=C2SC(SCSC#N)=NC2=C1 TUBQDCKAWGHZPF-UHFFFAOYSA-N 0.000 description 1
- YIKWKLYQRFRGPM-UHFFFAOYSA-N 1-dodecylguanidine acetate Chemical compound CC(O)=O.CCCCCCCCCCCCN=C(N)N YIKWKLYQRFRGPM-UHFFFAOYSA-N 0.000 description 1
- VKVLTUQLNXVANB-UHFFFAOYSA-N 1-ethenyl-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C=C VKVLTUQLNXVANB-UHFFFAOYSA-N 0.000 description 1
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical group OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- LJYOFQHKEWTQRH-UHFFFAOYSA-N 2-bromo-1-(4-hydroxyphenyl)ethanone Chemical compound OC1=CC=C(C(=O)CBr)C=C1 LJYOFQHKEWTQRH-UHFFFAOYSA-N 0.000 description 1
- DHVLDKHFGIVEIP-UHFFFAOYSA-N 2-bromo-2-(bromomethyl)pentanedinitrile Chemical compound BrCC(Br)(C#N)CCC#N DHVLDKHFGIVEIP-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- OIWXLVBZDMAARO-UHFFFAOYSA-N 2-decylsulfanylethanamine Chemical compound CCCCCCCCCCSCCN OIWXLVBZDMAARO-UHFFFAOYSA-N 0.000 description 1
- HFOCAQPWSXBFFN-UHFFFAOYSA-N 2-methylsulfonylbenzaldehyde Chemical compound CS(=O)(=O)C1=CC=CC=C1C=O HFOCAQPWSXBFFN-UHFFFAOYSA-N 0.000 description 1
- 229940044120 2-n-octyl-4-isothiazolin-3-one Drugs 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
- C23F11/143—Salts of amines
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
- C23F11/163—Sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/187—Mixtures of inorganic inhibitors
- C23F11/188—Mixtures of inorganic inhibitors containing phosphates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
- C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
Definitions
- This invention relates generally to novel methods, apparatuses, and compositions of matter useful in controlling the growth of organisms within slurry transporting pipelines. As described for example in US Patents 8,168,071,
- microbial growth and activity can create severe operational, environmental, and human safety problems in slurry pipelines. Problems caused or intensified by microbial growth and activity includes corrosion, solids production, hydrogen sulfide (H 2 S) generation, and contamination of the slurry.
- the microorganisms responsible for these problems can be both aerobic and anaerobic and include oxygen-reducing and sulfate-reducing bacteria. As the slurry water often comprises reservoir or seawater it will typically contain both problematic bacteria as well as required nutrients.
- a number of prior art methods have been proposed for addressing microbiological infestations of pipelines which include: temperature control, metabolite removal, pH control, Eh control, radiation, filtration, salinity control, chemical control (e.g., oxidizers, biocides, acids, alkalis), solids control (e.g., pigging or scraping the internal pipeline), and bacteriological controls (e.g., bacteria phages, enzymes, parasitic bacteria, monoclonal antibodies, competitive microflora).
- Some of these methods will kill the microorganisms, while others stress or disturb them sufficiently to inhibit their activity. Unfortunately none of these methods present many downsides. Moreover, they are not optimized for the specific conditions and requirements inherent in infestations within slurry transporting pipelines.
- At least one embodiment of the invention is directed towards a method of reducing the presence of microorganisms from a slurry transporting pipeline.
- the method comprises the steps of: adding an oxidizing biocide to a fluid in an amount higher than the oxidant demand of the pipeline, adding a non-oxidizing biocide to a fluid in an amount less than 30% of the minimum necessary to sterilize the microbiological organisms present before the oxidizing biocide was added, and feeding the fluid into the pipeline.
- the fluid may enter the pipeline after the biocides have been added.
- the fluid may be a plug, river water, freshwater, and/or seawater.
- the oxidizing biocide may be one selected from the list consisting of: chlorine dioxide, chlorine gas, hypochlorous acid, bromine derived biocides, and any combination thereof.
- the oxidizing biocide may be a reaction product of metal chlorate, hydrogen peroxide, and an acid selected from mineral acid, chlorous acid, and any
- the method may further comprise adding a corrosion inhibitor to the fluid, wherein but for the presence of the non-oxidizing biocide, the corrosion inhibitor would have been rendered ineffective by the oxidizing biocide.
- the pipeline may suffer no more corrosion-erosion than it would have had the corrosion inhibitor been added to the fluid in the absence of the oxidizing biocide and/or the non-oxidizing biocide.
- At least a portion of the pipeline in contact with the fluid may be constructed essentially out of mild steel and the presence of the oxidizing biocide reduces biocorrosion and substantially does not cause corrosion.
- the dosage of the biocides may be such that it reduces biocorrosion at the distal end of the pipeline while substantially not increasing corrosion at the proximal end of the pipeline.
- the dosage of oxidizing biocide to the fluid may be 1-10 ppm and the dosage of non- oxidizing biocide to the fluid may be 1-200 ppm more preferably between 50 - 120 ppm.
- the majority of the pipeline may be in contact with the fluid and/or may be constructed essentially out of mild steel and the presence of the oxidizing biocide reduces biocorrosion and does not cause corrosion.
- the method may exclude the presence of a nitrogenous bromine compound.
- FIG. 1 is an illustration of a slurry pipeline within which the invention is applied.
- FIG. 2 is microscopy pictures (40 x magnification) showing differences between a still polished-protected surface (top) and a coarse surface damaged by corrosion (bottom).
- FIG. 3 is a microscopy picture (40 x magnification) showing the aspect of a protected surface at the end of a corrosion evaluation trial (Test 14).
- Comminuted means powdered, pulverized, ground, or otherwise rendered into fine solid particles.
- Consisting Essentially of means that the methods and compositions may include additional steps, components, ingredients or the like, but only if the additional steps, components and/or ingredients do not materially alter the basic and novel characteristics of the claimed methods and compositions.
- Biocorrosion means corrosion resulting from the presence and activities of microorganisms which induce, accelerate, and/or maintain a corrosion reaction in a solid surface (such as metal)-fluid interface, typically conditioned by a biofilm, its rate and effects are influenced by the type/composition of the solid surface and/or fluid, the arrangement of the microorganisms on the solid surface, and/or the metabolic activity of the microorganisms.
- Corrosion means a chemical process which takes place on the surface of the solid material in contact with a fluidic medium, the process causes a loss of material from the surface to the medium, it may be the result of an anodic - cathodic type reaction caused between iron and water, it excludes erosion type processes.
- Corrosion-Erosion means a process in which both corrosion and erosion are occurring simultaneously, often corrosion-erosion results in a synergistic effect resulting in greater mass loss than the sum of the corrosion with the erosion expected for a given medium.
- Corrosion Inhibitor means a composition of matter known in the art to inhibit the rate of corrosion on a surface in contact with a corrosive fluid.
- Erosion means a physical abrasive process which takes place on the surface of the solid material in contact with a fluidic medium, the process causes a loss of material from the surface to the medium, and it excludes corrosion type processes.
- Hard means the measure of how resistant a particular kind of solid matter is to various kinds of permanent shape change when a force is applied, hardness is generally characterized by strong intermolecular bonds, but the behavior of solid materials under force is complex; therefore, there are different
- measurements of hardness including: scratch hardness, indentation hardness, and rebound hardness.
- Microorganism means any organism small enough to insinuate itself within, adjacent to, on top of, or attached to equipment used in or connected to a slurry transporting pipeline, it includes but is not limited to those organisms so small that they cannot be seen without the aid of a microscope, collections or colonies of such small organisms that can be seen by the naked eye but which comprise a number of individual organisms that are too small to be seen by the naked eye, as well as one or more organisms that can be seen by the naked eye, it includes but is not limited to any organism whose presence, in some way impairs the transport or value of the slurry, it also includes but is not limited to iron-oxidizing, sulfate reducing, and sulfur-oxidizing microorganisms.
- Mild Steel means an iron alloy that contains less than 1.65% of manganese, less than 0.60% of silicon and less than 0.60% of copper, and has a carbon content of between 0.05% and 0.29%
- mild steel includes steel alloys with no minimum amount of chromium, cobalt, molybdenum, nickel, niobium, titanium, tungsten, vanadium or zirconium, or any other element. Usually carbon content is between 0.05% and 0.29%. Mild steel undergoes more corrosion under such atmospheric conditions than when compared to stainless steel (which has for instance higher nickel and chromium content) does.
- Plug means a fluid under flux in a slurry pipeline that is either substantially free of all but trace or residual amounts of slurry or suspended solids; plugs are sometimes used when it is desired to keep the pipeline under flux but also not pass slurry to the terminus of the pipeline, plug fluids may comprise but are not limited to one or more of: water, reservoir water, seawater, sewer water, lake water, cooling tower water, boiler water, make down water, wastewater, and water separated from slurry.
- “Separation” means a mass transfer process that converts a mixture of substances into two or more distinct product mixtures, at least one of which is enriched in one or more of the mixture's constituents, it includes but is not limited to such processes as: Adsorption, Centrifugation, cyclonic separation, density based separation, Chromatography, Crystallization, Decantation, Distillation, Drying, Electrophoresis, Elutriation, Evaporation, Extraction, Leaching extraction, Liquid- liquid extraction, Solid phase extraction, Flotation, Dissolved air flotation, Froth flotation, Flocculation, Filtration, Mesh filtration, membrane filtration,
- Slurry means medium comprising a fluidic carrier within which is suspended a number of solid particles
- the solid particles include but are not limited to ground rock such as ore, coal ore, bauxite, iron ore, and the like and the fluid is often a liquid such as water, the amount of solid is such that the fluidic carrier has properties associated with a fluid thicker than the carrier alone
- slurries include but are not limited to dispersions, solutions, and can have liquid or water carrier fluids.
- Solids % means the portion of an aqueous system by weight that is silica bearing particles of the continuous phase.
- Thickener or “Settler” means a vessel used to effect a solid-liquid separation of a slurry, often with the addition of flocculants, the vessel constructed and arranged to receive a slurry, retain the slurry for a period of time sufficient to allow solid portions of the slurry to settle downward (underflow) away from a more liquid portion of the slurry (overflow), decant the overflow, and remove the underflow.
- Thickener underflow and thickener overflow are often passed on to filters to further separate solids from liquids.
- Under Flux means a having a fluid (including but not limited to slurry fluid, liquid fluid, water, and any combination thereof) actively passing through a system such as a pipeline.
- Water Soluble means materials that are soluble in water to at least 3%, by weight, at 25 degrees C.
- At least one embodiment of the invention is directed to a method which minimizes the infestation of one or more microorganisms within pipelines during ore slurry transport.
- slurry transport pipelines are often kept under flux for large periods of time (sometimes substantially most or essentially all, of the time). This often results in the pipeline needing to remain under flux even after the pipeline terminus (such as a refinery or smelter) has absorbed the maximum amount of slurry it can (or its operator wishes to) handle.
- plugs are low value bulk materials that are often discarded after passage through the pipeline, plugs are often unclean and are a vector for introducing microorganisms into slurry pipelines.
- a fluid is pre-treated to remove microorganisms before it is fed into a pipeline.
- the fluid may become plug fluid and/or slurry fluid.
- the pre-treatment is tailored for use in a pipeline. Problems innate to pipelines that differ from other industrial process streams result from the sheer distances that the fluid traverses. It is extremely difficult for a biocide to remain chemically active in a fluid after it has traveled tens, hundreds, possibly thousands of miles. As a result according to the prior art, either expensive biocide introduction systems must be located throughout the length of the pipeline and must utilize complicated equipment to coordinate the biocide feed with the pipeline fluid flow, or huge quantities of biocide must be introduced into the fluid.
- the prior art leaves users with an unacceptable tradeoff; the pipeline operator must either accept excessive microorganism infestation or excessive pipe corrosion. Even worse the operator may have to make a tradeoff between protecting different portions of the pipeline. For example, adding sufficient oxidizing biocide that is still active when it reaches a more distal (such as by the terminus) point of the pipeline can only be accomplished by dosing concentrations highly corrosive to a more proximal (such as by the fluid entry point) point.
- the fluid is treated in a manner that both prevents microorganism infestation and does not corrode (or excessively corrode) the pipeline.
- the method may involve: treating the fluid with an oxidizing biocide, treating the fluid with a non-oxidizing biocide after the oxidizing biocide, and feeding the fluid into a slurry transport pipeline.
- the amount of oxidizing biocide may be sufficient to eliminate substantially all of the microorganisms in the fluid.
- the amount of non-oxidizing biocide may be in an amount sufficient to neutralize the oxidizing biocide but insufficient to eliminate substantially most of the microorganisms that had previously been in the fluid.
- the non-oxidizing biocide may prevent any further contamination while the plug of water is pumped through the pipeline.
- Biocides are often classified as oxidizing or non-oxidizing, depending on their chemical composition and mode of action. Typically when oxidizing biocides are used in microbiological control programs in other process systems they are applied in such a manner as to apply quantities sufficient to maintain a free oxidizer residual in the process. This can be problematic in process liquids in slurry transport pipelines because they contain high concentrations of dissolved and particulate inorganic and organic materials. Such process waters exhibit a high and variable "demand" on the oxidizer (i.e., the oxidizer can react with the inorganic and organic materials and be rendered ineffective as a biocide). Also, the excess of oxidizing biocide could corrode the mild steel pipeline making the treatment pointless.
- oxidizing biocides are consumed by inorganic species such as ferrous iron, reduced manganese, sulfides, sulfites, etc. as well as organic compounds such cellulosic fibers and additives.
- inorganic species such as ferrous iron, reduced manganese, sulfides, sulfites, etc.
- organic compounds such cellulosic fibers and additives.
- these pipelines are especially inhospitable to oxidizing biocides due to high "demand".
- oxidizer stabilizers such as nitrogenous bromine compounds.
- At least one embodiment includes the presence of oxidizer stabilizers including but not limited to nitrogenous bromine compounds.
- At least one embodiment excludes the presence of oxidizer stabilizers including but not limited to nitrogenous bromine compounds.
- oxidizer stabilizers including but not limited to nitrogenous bromine compounds.
- Non-oxidizing biocide useful in the invention include, but are not limited to, aldehydes, formaldehyde releasing compounds, halogenated
- aldehyde containing compounds can be linear, branched or aromatic.
- the formaldehyde releasing compounds are preferably halogenated, methylated nitro- hydrocarbons, for example 2-bromo-2-nitro-propane-l ,3-diol (Bronopol).
- the amides are preferably halogenated, for example 2,2-dibromo-3-nitrilopropionamide (DBNPA).
- the heterocyclic compounds useful in the invention include thiazole and isothiazolinone derivatives. Some examples of heterocyclic compounds include, but are not limited to, 5-chloro-2-methyl- 4-isothiazolin-3-one (CMIT) and 2-methyl-4- isothiazolin-3-one ( ⁇ ).
- the surface active agents useful in the invention include detergents, wetting agents and emulsifiers.
- Some examples of surface active agents include, but are not limited to, long chain quaternary ammonium compounds, aliphatic diamines, guanidines and biguanidines.
- non-oxidizing biocide useful in the invention include, but are not limited to, 2-methyl-4-isothiazolin-3-one (MIT); 5- chloro-2-methyl-4-isothiazolin-3-one (CMIT); 2-n-octyl-4- isothiazolin-3-one; 4,5- dichloro-2-(n-octyl)-4-isothiazolin-3-one; 1 ,2-benziosthiazolin-3-one;
- MIT 2-methyl-4-isothiazolin-3-one
- CMIT chloro-2-methyl-4-isothiazolin-3-one
- 2-n-octyl-4- isothiazolin-3-one 2-n-octyl-4- isothiazolin-3-one
- 4,5- dichloro-2-(n-octyl)-4-isothiazolin-3-one 1 ,2-benziosthiazolin-3-one
- decylthioethylamine 2-bromo-2-nitropropane- 1 ,3-diol; ⁇ -dodecylguanidine hydrochloride; n-dodecylguanidine acetate; l-(3-chloroallyl)-3,5,7-triaza-l- azoniaadamantane chloride; 1 ,2-dibromo-2,4-dicyanobutane; bis(l ,4- bromoacetoxy)-2-butene; bis(l ,2-bromoacetoxy)ethane;
- the oxidizing biocide and/or the method of its introduction is one or more of those described in one or more of US Patents 5,895,638, 6,387,344, 7,070,710, 6,790,427, and 7,682,592.
- the oxidizing biocide is and/or comprises chlorine dioxide, chlorine gas, hypochlorous acid, bromine derived biocides, and any combination thereof.
- Chlorine dioxide may be produced by prior (before introduction to the fluid) or in situ (within the fluid) reduction of chlorate ions with a peroxide (such as hydrogen peroxide) in the presence of an acid (such as but not limited to sulfuric acid and/or hydrochloric acid).
- the chlorate ions may be derived from metal chlorates.
- the oxidizing biocide may further comprise one or more of: a protective colloid, a radical scavenger, and/or a complexing agent. The ratio of chlorate to peroxide may range from 1: 10 to 10: 1.
- the oxidizing biocide is dosed into the fluid in an amount that is sufficient to sterilize the fluid.
- this may be 1- 50 ppm oxidant (for example 1-50 ppm chlorine dioxide).
- the non-oxidizing biocide is then dosed in an amount of l -30 of the amount needed to sterilize the fluid (many non-oxidizing biocides sterilize at 500-350 ppm so the dosage may be as low as 5-200 more preferably 5-120 ppm or more or less).
- the non-oxidizing biocide is added: 1) to prevent further contaminations, 2) to eliminate all traces of the oxidazing biocide and therefore prevent corrosion, and/or 3) to exterminate any microorganism already within the pipeline.
- the non-oxidizing biocide may eventually eliminate a few microorganisms that somehow have survived the oxidizing biocide but this is not its primary function.
- the first oxidizing treatment eliminates much of the microorganisms. Its combination with the non-oxidizing biocide drastically reduces the oxidative potential of the oxidizing biocide (possibly by reduction). This results in two benefits. First it reacts much more slowly and persists through a long length of the pipeline. Second its lower activity makes it less likely or not likely at all to corrode the pipeline. While the reduced activity oxidizing biocide might not have been effective on the original microorganism population present in the original fluid source, because it has some time to operate on those microorganisms before the addition of the reducing biocide, the only remaining population in the pipeline is a small number of survivors that the low activity oxidizing biocide can more than handle.
- the less active oxidizing biocide will react less with the inorganic materials prevalent in the pipeline and therefore can make use of the prolonged contact time with the microorganisms to eliminate them.
- the invention is especially suited to the specific conditions in a slurry transport pipeline. Potentially any microorganism that is resistant to oxidizing biocide is unlikely to be resistant to non-oxidizing biocide. Thus it is a good strategy use two kinds of biocides in one system.
- a corrosion inhibitor in addition to the biocide(s), also added to the pipeline is a corrosion inhibitor.
- corrosion inhibitors include but are not limited to those described in US Patent 8,557,338.
- the oxidizing biocide would have impaired and/or completely disabled the corrosion inhibitor, but instead the biocide does not (or does less) inhibit the effectiveness of the corrosion inhibitor.
- the corrosion inhibiter is a composition comprising: at least 60% water, 1-20% zinc compound and 1-20% phosphoric acid or phosphate compounds or any phosphorous compound, and/or it may comprise an oxygen scavenger including but not limited to sodium bisulfate.
- Representative zinc compounds include but are not limited to zinc chloride, zinc oxide, zinc sulfate, zinc phosphate, and the like, and any combination thereof.
- the corrosion inhibiter is a composition comprising at least one of: methoxypropylamine and monoethanolamine.
- the corrosion inhibitor of the invention comprises a product of dimethylaminoethoxyethanol, dimethylethanolamine, tall oil, C18-unsaturated fatty acid trimers, and branched dodecylbenzenesulfonic acid (DDBSA).
- DBSA dodecylbenzenesulfonic acid
- the corrosion inhibitor of the invention comprises a product of tall oil, reaction products with 2- [2-
- alkanolamines include N,N-dimethylethanolamines, such as (N,N-dimethylaminoethoxy)ethanol; dimethylethanolamine;
- triethanolamine triethanolamine
- methyldiethanolamine ethanolamine
- diethanolamine other cyclic amines including morpholine, methylmorpholine, ethylmorpholine, piperidine, alkylpiperidines, piperazine, alkylpiperazines; ethyleneamines including DETA, TETA, TEPA, and the like; alkylamines including methylamine, dimethylamine, alkylmethylamines, dimethylalkylamines; methylaminopropylamine;
- dimethylaminopropylamine dimethylaminoethylamine; methylaminoethylamine; the like; and combinations thereof.
- Representative fatty acids include trimeric CI 8 unsaturated fatty acid (e.g., CAS 68937-90-6), dimer acids, polymerized tall-oil fatty acids, one or more components of a crude tall oil composition, branched DDBSA, the like, and any combination of the foregoing.
- trimeric CI 8 unsaturated fatty acid e.g., CAS 68937-90-6
- dimer acids dimer acids
- polymerized tall-oil fatty acids one or more components of a crude tall oil composition
- branched DDBSA branched DDBSA
- a crude tall oil composition may include abietic acid; neoabietic acid; palustric acid; pimaric acid; dehydroabietic acid; palmitic acid; stearic acid; palmitoleic acid; linoleic acid; 5,9,12- octadecatrienoic acid; linolenic acid; 5,11,14-eicosadienoic acid; cis,cis-5,9- octadecadienoic acid; eicosadienoic acid; elaidic acid; cis-l,l-octadecanoic acid, C20-C24 saturated acids; the like; and any combination of the foregoing.
- the corrosion inhibitor composition of the invention includes the following formula (1) using dimethylalkanolamines with trimer acid [CAS 68937-90-6].
- the corrosion inhibitor composition of the invention includes the following formula (2) dimethylalkanolamines with trimer acid [CAS 68937-90-6].
- trimer acid contains variable percentages of dimers and trimers, adding to the complexity.
- a typical composition can include approximately 40% dimer and 60% trimer with insignificant percentages of the monomer.
- the corrosion inhibitor composition of the invention includes the following formula (3) using dimethylalkanolamines with tall oil [CAS 8002-26-4].
- the corrosion inhibitor composition of the invention includes the following formula (4) using dimethylalkanolamines with tall oil [CAS 8002-26-4].
- the second group of salts which can form in this blend is with tall oil, exemplified in formulas (3) and (4) above.
- Crude tall oil is, for example, a byproduct of the pulp and paper industry and yields another complex mixture of fatty acids, rosin acids, and lesser amounts of terpenes and sterols.
- the composition of tall oil is variable with differences seen in regional sources and manufacturing processes as well as seasonal influences. Crude tall oil and distilled tall oil can also be very different. These differences are well known in the art.
- the structures above provide a representation of the salts formed from dimethylalkanolamines and tall oil (oleic acid is shown).
- the structures below provide representative examples of the various acids present in this mixture:
- Tall oil fatty acids include 5,9,12- octadecatrienoic acid; linolenic acid; 5,11,14-eicosatrenoic acid; cis,cis-5, 9- octadecadienoic acid; eicosadienoic acid; elaidic acid; cis-l l-octadecanoic acid; and C20, C22, C24 saturated acids.
- Tall oil fatty acids may comprise any combination of the foregoing examples and others known in the art.
- the corrosion inhibitor composition of the invention includes the following formula (5) using dimethylalkanolamines with branched dodecylbenzene sulfonic acid [CAS 68411-32-5].
- the corrosion inhibitor composition of the invention includes the following formula (6) using dimethylalkanolamines with branched dodecylbenzene sulfonic acid [CAS 68411-32-5].
- DBSA dodecylbenzene sulfonic acid
- the product of the invention comprises about 10 wt to about 100 wt active ingredient.
- the amount of active is from about 10 wt to about 36 wt .
- the amount ranges from about 15 wt to about 30 wt active.
- the product comprises about 27 wt of the active.
- the corrosion inhibitor composition of the invention may include at least one solvent.
- Representative solvents include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, aromatic
- hydrocarbons isoparaffinic solvents, monoethyleneglycol, ethylene glycol monobutyl ether, the like, water (water can also be used to emulsify the corrosion inhibitor), and combinations thereof.
- a solvent component aids in corrosion inhibitor delivery and helps provide desirable secondary properties of the product, such as desired viscosity, temperature stability, and the like.
- the amount of solvent may range from about 8.5 wt to about 90 wt . In other embodiments, the amount of solvent may range from about 30 wt to about 40 wt%.
- the corrosion inhibitor composition of the invention may include at least one dispersant.
- the dispersant is preferably an oxyalkylate polymer (i.e., polyoxyethylene) such as ethoxylated sorbitan
- monolaurate This may include varying oxyalkylated sorbitan esters (e.g., mono, di- , and tri-esters) and non- oxyalkylated sorbitan esters as well.
- the amount of polyoxyalkylate can vary from about 1-2 mol up to about 80 mol , preferably 20 mol .
- the amount of oxyalkylated sorbitan esters in the final product ranges from about 1 wt to about 10 wt%, preferred about 1 wt to about 5 wt .
- the corrosion inhibitor composition of the invention further comprises at least one quaternary ammonium compound in the range of about 5-35 wt%, preferred about 5-20 wt%.
- the corrosion inhibitor composition of the invention includes at least one solvent and at least one dispersant.
- the microbiological activity of the fluid is measured by a suitable device located at one or more points before, along, or downstream from the pipeline.
- suitable devices include those described in US Patents 8,012,758, 7,981,679, 7,949,432, 8,613,837, and US Patent Applications 14/138,526 and 13/657,993.
- the feed mechanism of one or more of the biocides and/or corrosion inhibitors is at least partially automated and controlled by process logic which evaluates the
- measurements from a suitable device and appropriately feeds, ceases feeding, and/or adjusts feed amounts, rates, dosages, and/or concentrations accordingly.
- the pH of the media is adjusted to values between 10.0 and 4.0, more preferably between 5.0 and 8.0 and even more preferably between 6.0 and 7.5.
- the pH adjustment can be carried out in any practical manner including but not limited to one or more metal hydroxide, and/or a carbonate or a bicarbonate of any metal including but not limited to calcium, sodium, potassium, and any combination thereof. pH adjustment may also be achieved by using any molecule with alkaline or basic (non-acidic) characteristics like ammonia, amines and hydroxyl compounds alone or in any combination of the aforementioned.
- Representative examples of pH adjustors include but are not limited to sodium hydroxide, sodium carbonate, calcium hydroxide, and any combination thereof.
- the invention has the advantage of allowing for the construction and continuous use of pipelines with cheaper materials than biocorrosion resistant steels. It also eliminates the need of coating mild steel pipelines built for ore slurry transport and it can be used in existing pipelines as mild steel pipelines.
- the invention allows for the use of strong oxidizing biocides to treat the water pumped in a mild steel pipeline which, along with the use of non-oxidizing biocide, guarantees good microbiological control, no corrosion issues and lower total biocide consumption.
- Example 1 Microbiological efficiency of treatment with oxidizing biocide compared to non-oxidizing biocide.
- Example 2 Corrosion rate increase due presence of oxidizing biocide C1 2 0.
- the tubular coupons received a surface treatment after each electrochemical experiment in order to remove any corrosion product eventually deposited on the surface before being weighted.
- the electrodes were copiously rinsed with taped water, smoothly brushed and then immersed into concentrated hydrochloric acid for 5 seconds. Finally, the electrodes were copiously rinsed with distilled water, dried and weighted.
- W Wi - W2 (5) where: W: total weight loss
- Corrosion rate can be obtained according the equation (6):
- CR is the corrosion rate without any treatment and CRCI is the corrosion rate determined in the presence of corrosion inhibitor.
- Diagnosis between localized and general corrosion can be accomplished through surface examination before and after each trial. This exam was recorded using regular digital camera and microscopy with 40x or lOOx magnification lens. This qualitative method is extremely useful to evaluate the performance of corrosion inhibitor especially when localized corrosion or pitting is taking place.
- Corrosion inhibitor composition in this case was based on zinc compounds and phosphate compounds.
- Test 8 the untreated water is corrosive to mild steel.
- the use of corrosion inhibitor can reduce this effect (Test 9) but the presence of oxidizing biocide (Test 10 and 11) even at lower dosage (Test 13) increases the corrosion rate.
- FIG. 2 illustrates the differences between a protected surface (Test 9) and a corrosion damaged surface (Test 10).
- Example 3 Effect of combined oxidizing biocide C1 2 0 and non-oxidizing biocide over corrosion rate in presence of corrosion inhibitor.
- oxidizing biocide may be beneficial from the perspective of microbiological control (Table 1) but is clearly detrimental from the perspective of corrosion rate (Table 2).
- Table 3 shows the results obtained for corrosion rate of mild steel using oxidizing biocide followed by a non-oxidizing biocide. Each water sample was treated with chlorine dioxide for ten minutes and then treated with non-oxidizing biocide, corrosion inhibitor and lime (calcium hydroxide) for pH adjustments.
- Non oxidizing biocide is Sodium dimethyldithiocarbamate + Disodium
- the invention encompasses any possible combination of some or all of the various embodiments mentioned herein, described herein and/or incorporated herein.
- the invention encompasses any possible combination that also specifically excludes any one or some of the various embodiments mentioned herein, described herein and/or incorporated herein.
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US14/252,709 US9909219B2 (en) | 2014-04-14 | 2014-04-14 | Slurry biocide |
PCT/US2015/022783 WO2015160487A1 (en) | 2014-04-14 | 2015-03-26 | Slurry biocide |
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EP3131854A1 true EP3131854A1 (en) | 2017-02-22 |
EP3131854A4 EP3131854A4 (en) | 2018-01-10 |
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EP (1) | EP3131854B1 (en) |
CN (1) | CN106170458B (en) |
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BR (1) | BR112016024040B8 (en) |
CL (1) | CL2016002609A1 (en) |
MA (1) | MA39831A (en) |
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KR102623640B1 (en) * | 2020-07-22 | 2024-01-11 | 삼성에스디아이 주식회사 | Cmp slurry composition for polishing tungsten pattern wafer and method for polishing tungsten pattern wafer using the same |
US20220204370A1 (en) * | 2020-12-29 | 2022-06-30 | Ecolab Usa Inc. | Method for controlling odor and taste producing metabolites in water systems through use of primary and secondary oxidation processes |
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2014
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WO2015160487A1 (en) | 2015-10-22 |
EP3131854B1 (en) | 2022-04-27 |
MA39831A (en) | 2017-02-22 |
CN106170458B (en) | 2020-02-07 |
US20150291462A1 (en) | 2015-10-15 |
US9909219B2 (en) | 2018-03-06 |
BR112016024040A2 (en) | 2017-08-15 |
CN106170458A (en) | 2016-11-30 |
BR112016024040B8 (en) | 2023-01-17 |
BR112016024040B1 (en) | 2022-02-01 |
SA516380063B1 (en) | 2020-07-09 |
AU2015248151B2 (en) | 2018-11-15 |
CL2016002609A1 (en) | 2017-11-03 |
AU2015248151A1 (en) | 2016-10-20 |
EP3131854A4 (en) | 2018-01-10 |
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